Sulfinyl ylids

ABSTRACT

IN WHICH R AND R&#39;&#39; ARE HYDROCARBON GROUPS OR HYDROCARBON GROUPS WITH INERT SUBSTITUENTS AND Z IS NITROGEN OR CARBON JOINED TO AN ELECTRON WITHDRAWING GROUP CAN BE MADE BY REACTING THE APPROPRIATE SULFINYL CHLORIDE WITH A COMPOUND R&#39;&#39;3P=ZH IN THE PRESENCE OF AN ACID ACCEPTOR INERT TO RSOCI.   R-SO-Z=P(-R&#39;&#39;)3   SULFINYL YLIDS WHICH ARE USEFUL AS ACID SCAVENGERS HAVING THE FORMULA

United States Patent Office 3,647,856 SULFINYL YLIDS Alden Dwayne Josey,New Castle County, Del., assignor to Egidu Pont de Nemours and Company,Wilmington, e No Drawing. Filed Dec. 8, 1967, Ser. No. 688,958 Int. Cl.C07c 145/00 US. Cl. 260-465 U 7 Claims ABSTRACT OF THE DISCLOSURE FIELDOF THE INVENTION This invention relates to new sulfinylcarbon-phosphorus and nitrogen-phosphorus ylids.

SUMMARY OF THE INVENTION The present invention comprises novel compoundshaving the formula R--z=1 Ra 1 wherein Z is N or CX, X being an electronwithdrawing group such as CN, -COOR', 'COR", CO e )2, s 4. 2, s 4 2 s 5C H or the like.

In the above formulae:

R is a hydrocarbyl group of 1-18 carbon atoms free of ethylenic oracetylenic unsaturation or such hydrocarbyl group having heterocyclicoxygen, lower alkoxy or halogen substituents.

R is a hydrocarbyl group of 1-18 carbon atoms free of ethylenic oracetylenic unsaturation or such hydrocarbyl group having lower alkoxysubstituents.

R" is H or R.

In the above lower denotes that the alkyl group contains [from 1 to 6carbon atoms including straight chain and branched alkyl groups. Theterm halogen includes fluorine, chlorine, bromine and iodine.

The above compounds of Formula I can be made by reaction, in solution inan inert organic solvent, of a sulfinyl chloride having the formula 0n-s-oi 11 with a compound having the formula R P=ZH (111) at atemperature of -25 C. to 75 C., preferably from 0 to 25 C., in thepresence of an acid acceptor, and recovering a compound having FormulaI.

DETAILED DESCRIPTION OF THE INVENTION The compounds of the presentinvention can be made by contacting and reacting a compound having theformula R' P=ZH with a sulfinyl chloride RSOC1 in the presence of anacid acceptor. In the case in which Z is nitrogen, the compounds R' P=ZHare themselves suitable acid acceptors and no further base is needed.When 3,647,856 Patented Mar. 7, 1972 Z is a carbon atom activated by anelectron withdrawing group X, an additional acid acceptor is required.Such acid acceptor must be inert to the reactants and the products.Suitable acid acceptors are tertiary amines including heterocyclictertiary amines such as trialkylamines, pyridine, quinoline and thelike.

The reaction is preferably conducted in an inert solvent for thereactants. Suitable solvents include aromatic and aliphatic hydrocarbonsor such hydrocarbons substituted with halogen, or alkoxy groups; ethers,ketones and esters. Tertiary amines, which act as acid acceptors arealso useful as solvents for the reaction.

The process is operable at temperatures of -25 C. to C., but forconvenience and good yields it is generally preferred to conduct thereaction at 0 to 25 C. The reaction can be suitably run at about 0 C. bycooling the vessel containing the reactants in an ice bath.

Pressure is not critical. Pressures below 1 atmosphere or pressureshigher than 1 atmosphere can be employed.

In selecting solvents, acid acceptors and the condition of the reaction,it is preferred that the reaction mixture should not boil, i.e., if lowpressures are used, a high boiling solvent is selected, which does notboil at the selected temperature and pressure.

The proportions of reactants can vary Widely thus the ratio of ZH=PR' toRSOCl can be from 20:1 to 1:10, although these limits are not critical.It is preferred to employ stoichiometric proportions, i.e., a ratio ofabout ZH PR' /R'SOCI of 2:1 when Z is N and 1:1 when Z is CX, foreconomy in the use of the reactants.

The new compositions are generally crystalline solids which have thecapacity to absorb two equivalents of acid per mole. They are,therefore, useful as acid scavengers in aqueous or organic fluidsystems. The compounds of the present invention are also useful asthermal stabilizers for polymers such as polyvinyl chloride whichrelease acid on degradation.

This invention is further illustrated by the following examples, whichshould not, however be construed as fully delineating the scope of thisdiscovery.

EXAMPLE 1 (Carbomethoxy-p-toluenesu1finylmethylene) triphenylphosphoraneA solution of 7.58 g. (0.023 mole) of(carbomethoxymethylene)triphenylphosphorane and 3.2 ml. (2.3 g., 0.023mole) of triethylamine in 200 ml. of anhydrous benzene was stirred at 0C. while 3.96 g. (0.023 mole) of ptoluene sulfinyl chloride in 25 ml. ofbenzene was added during 0.5-1.0 hour. A precipitate of triethylaminehydrochloride separated immediately. The mixture was stirred for 3 hoursand allowed to Warm gradually to 25 C. during the last hour. The aminesalt was collected, washed with fresh benzene, and dried in vacuo. Theyield was 3.05 g. (96.5%). The filtrate was evaporated under vacuum togive a pale straw-colored syrup which crystallized on addition of 15-20ml. of ethyl acetate and gentle warming. On filtration, there wasobtained 8.75 g. (80.5%) of (carbomethoxy-p-toluenesulfinylmethylene)triphenylphosphorane in the form of White crystals, M.P. 142-144 C. dec.A second crop (1.08 g.) was obtained on evaporation of the filtrate andtrituration of the residue with ethyl acetate. The total yield was 9.83g. (90.5%).

Recrysallization of a small sample from ethyl acetate gave colorlessmicroprisms, M.P. 145-l47 C. dec.

Analysis.Calcd. for C H O PS (percent): C, 71.2;

.H, 5.34; S, 6.79. Found (percent): C, 71.2; H, 5.42; S,

EXAMPLE 2 iBenzenesulfinylcarbomethoxymethylene triphenylphosphoraneUsing the procedure of Example 1, the reaction of (carbomethoxymethylenetriphenylphosphorane 16.72 g., 0.05 mole), triethylamine (7 ml., 0.05mole) and benzenesulfinyl chloride (8.0 g., 0.05 mole) in 400 ml. ofbenzene was carried out. There was obtained 22 g. (96% yield) of(benzenesulfinylcarbomethoxymethylene triphenylphosphorane, M.P. l20l2lC. dec. A sample twice-crystallized from ethyl acetate had M.P. 120-121"C. dec. and retained solvent of crystallization despite prolonged dryingin vacuo.

Analysis.Calcd. for C H O PS- /2(CH CO C H (percent): C, 69.3; H, 5.42;S, 6.38. Found (percent): C, 69.4; H, 5.46; S, 6.42.

EXAMPLE 3 (Cyano-p-toluenesulfinylmethylene) triphenylphosphoraneBenzenesulfinylcyanomethylene triphenylpho sphorane Using the procedureof Example 1, the reaction of (cyanomethylene)triphenylphosphorane 15.0g., 0.05 mole) triethylamine (7 ml., 0.05 mole) and benzenesulfinylchloride (8.0 g., 0.05 mole) in a mixture of 400 ml. of benzene and 75ml. of dichloromethane was carried out. There was obtained 21.2 g. (97%yield) of (benzenesulfinylcyanomethylene)triphenylphosphorane in theform of colorless crystals, M.P. 213-2l4 C. dec.

AnaIysis.Calcd. for C H NOPS (percent): C, 73.4; H, 4.74; S, 7.54. Found(percent): C, 73.5; H, 4.82; S

EXAMPLE 5 N-benzenesulfinyltriphenylphosphinimine A solution of 18mmoles of triphenylphosphinimine in 100 ml. of anhydrous benzene waschilled in ice and stirred while 1.4 g. (8.7 mmoles) of benzenesulfinylchloride in 10 ml. of benzene was added during 0.5 hour.

After an additional hour, the precipitated aminotriphenylphosphoniumchloride was collected, washed with benzene, and dried. The yield was2.73 g. (95.5% yield). The filtrate was evaporated to dryness, and thecrystalline residue was washed with hexane. There was obtained 2.9 g.(83% yield) of N-benzenesulfinyltriphenylphosphinimine in the form oflight tan crystals, Recrystallization from ethyl acetate gave largecolorless prisms, M.P. 157158 C. The melt showed only slightdecomposition at 250- 260" C. The mass spectrum showed low intensitypeaks at m./3 123 (PhSEN) and 278 (Ph PO).

,-lnalysis.-Calcd. for C H NOPS (percent): C, 71.8; H, 5.02; N, 3.49; S,7.99. Found (percent): C, 71.9; H, 4.79; N, 3.46; S, 8.12.

EXAMPLE 6 N-p-toluenesulfinyltriphenylphosphinimine A solution oftriphenylphosphinimine was prepared from 7.20 g. (0.023 mole) of theaminophosphonium salt in ml. of anhydrous benzene and 14.4 ml. of ca.1.6 M n-butyllithium in hexane. The imine solution was transferred byfiltration into a second vessel and chilled in an ice bath while 2.0 g.(0.0115 mole) of p-toluenesulfinyl chloride in 10 ml. of benzene wasadded during 15-20 minutes. The mixture was allowed to stir and warmgradually to 25 C. over a period of 3 hours. The workup was carried outas in Example 5, and from the filtrate there was obtained 4.25 g. (89%yield) of N-p-toluenesulfinyltriphenylphosphinimine in the form of thepale yellow crystals, M.P. 1121l6 C. A sample crystallized from ethylacetate had M.P. 118-119 C., and like the benzenesulfinyl derivative,showed surprising thermal stability at 250 C. and higher.

Analysis.Calcd. for C H NOPS (percent): C, 72.2; H, 5.34; S, 7.72. Found(percent): C, 72.0; H, 5.33; S, 7.66.

When the substituted phosphines shown in Column A of Table I areconverted to the corresponding phosphinimines by the procedure of Appel& Hauss, Chem. Ber. 93, 405-11 (1960), and the resulting phosphiniminesare substituted for triphenylphosphinimine in the procedure of Example5, the ylids shown in Column B are obtained.

When the sulfinyl chlorides shown in Column A of Table II aresubstituted for p-toluenesulfinyl chloride in the procedure of ExampleI, the ylids shown in Column .8 are obtained. The sulfinyl chlorides initems 9 to 11 are prepared from the corresponding sulfonic acids by theprocedure of Kurzer, Organic Syntheses, Collective vol. IV, pp. 937-939.

TABLE II Methylenetriphenylphosphorane Item Sulfinyl chloride product 1o-Toluenesulfinyl chloride.(Carbomethoxy-o-toluenesulfinylmethylene)triphenylphos phorane.

2 Methanesulfinyl chloride(Carbomethoxymethanesulfinylmethylene)triphenylphosphorane.

3 Pentanesulfinyl chloride...(Carbomethoxypentanesulfinylmethylcne)triphenylphosphorane.

4 2-naphthalenesulfiny1 (Carbomethoxy-2-napthalenesulchloride.fifiylmethylene)triphenylphosp orane. 5 p-Methoxybenzenesulfinyl(Carbomethoxy-p-methoxybenchloride.zene-sulfinylmethylene)triphenyl-phosphorane. 6 pChlorobenzenesulfinyl(Oarbomethoxy-p-chlorobenzenechloride.sulfinylmethylene)triphenylphosphorane.

7 p-Bromobenzenesulfinyl (Carbomethoxy-p-bromobenzenechloride.sulfinylmethylene)triphenylphosphorane.

8 p-Iodobenzenesulfinyl (Carbomethoxy-p-iodobenzenesulchloride.finylmethylene)triphenylphosphorane.

9 Oyclohexauesulfiuyl (Oarbomethoxycyclohexanesulchloride.fiihiylmethylene)triphenylphosp crane. 10 Octadecanesulfinyl(Carbomethoxyoctadecanesulfinylchloride. methylene)triphenylphosphorane.

11 2-benzofuransulfinyl (Carbomethoxy-2-benzofuransulchloride.finylmethylene)triphenylphosphorane.

When the substituted phosphoranes shown in Column A of Table III aresubstituted for (cyanomethylene)triphenylphosphorane in the procedure ofExample IV, the ylids shown in column B are obtained.

TABLE III Siflfinylmethylenephosphorane Item Substituted phosphoraneproduct 1 (Carbomethoxymethyl-(Benzenesulfinylcarbomethoxyene)-tricyclol1exylphosmethylene)tricyclohexylphosphorane.phorane.

2 (N,N-diphenylcarbamoyl-(Benzenesulfinyl-N,N-diphenylmethylene)triphenylcarbamoylmethylen'e)triphenylphosphorane.phosphorane.

3 (Carboethoxymethylene)-(Benzenesulfinylcarboethoxytrimethylphosphorane.mlethylenefirimethylphosp crane.

4 (Carboethoxymethylene)-(Benzenesulfinylcarboethoxytrihexylphosphorane. niethylenefirihexylphosporane.

5 (Carboethoxymethylene)-(Benzenesulfinylcarboethoxytridecylphosphorane.methylene)tridecylphosphorane.

6 (Oarboethoxymethylene)-(Benzenesulfinylcarboethoxytri-p-anisylphosmethylene)tri-p-anisylphosphorane.phorane.

7- (Formy1methylene)trl- (B enzenesulfinylformylmethylene)phenylphosphorane. triphenylphosphoraue.

8 (Acetylmethylene)tri- (Benzeneslflfinylacetyhnethylene)-phenylphosphorane. triphenylphosphorane.

9 (Chloroacetylmethylene)-(Benzenesulfinylchloroacetyltrlphenylphosphorane.niathylenefiriphenylphosp orane.

10 (Benzoy1methylene)tri-(Benzenesulfinylbenzoylmethylphenylphosphorane.ene)triphenylphosphorane.

11 (Methoxymethylene)tri-(Benzenesulfinylmethoxymethylphenylphosphorane.ene)triphenylphosphorane.

12 (But0xymethylene)tri- (Benzenesulfinylbutoxymethylphenylphosphorane.ene)triphenylphosphorane.

13 (p-Tolyloxymethylene)-(Benzenesulfinyl-p-tolyloxytriphenylphosphorane.mlgthylenenriphenylphosp crane.

14 (Diphenylphosphiuoxy-(Beuzenesulfinyldlphenylphosmethylene)triphenylphinoxymethy1ene)triphenylphosphorane.phosphorane.

15 (p-Nitrophenylmethyl-(Benzenesulfinyl-p-nitrophenylene)triphenylphosphormethylene)triphenylphosane.phoraue.

16- (p[Phenylsulfonyl]-(Benzenesulfinyl-p-[phenylsulphenylmethylene)trlfonyl]pheny1methyleue)triphenylphosphorane.phenylphosphorane.

17.. (Phenylmethylene)tri-(Benzenesulfinylphenylmethylphenylphosphoranea ene)triphenylphosphoraue.

As many apparently widely diiferent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound having the formula in which Z is N or CX, X being anelectron withdrawing group selected from the class consisting of -CN,-COOR', COR CONR OR,

R is a hydrocarbyl group of 1 to 18 carbon atoms free of ethylenic oracetylenic unsaturation or such hydrocarbyl group having heterocyclicoxygen, lower alkoxy or halogen substituents R is a hydrocarbyl groupfree of ethylenic or acetylenic or acetylenic unsaturation or suchhydrocarbyl group having lower alkoxy substituents R" is H or R.

2. Composition of claim 1 in which R is p-methylphenyl R is phenyl and Zis CCO CH 3. Composition of claim 1 in which R is p-methylphenyl R isphenyl and Z is CCN.

4. Composition of claim 1 in which R is phenyl R is phenyl and Z iS CCO2CH3.

5. Composition of claim 1 in which R is phenyl R is phenyl and Z is CON.

6. Composition of claim 1 in which R is phenyl R is phenyl and Z is N.

7. Composition of claim 1 in which R is p-methylphenyl R is phenyl and Zis N.

References Cited UNITED STATES PATENTS 3,253,028 5/1966 Louthan 260-551HENRY R. JILES, Primary Examiner H. I. MOATZ, Assistant Examiner US. Cl.X.R.

I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 856Dated March 7 1 q p Inventofls) Alden Dwayne Josey It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Col. 3, line 45, change "C to C Col. 6, line' 20, "-COR should bechanged to -COR" Signed and sealed this 8th day of August 1972.

(SEAL) A'ttest:

EDWARD I LFLETCHEIRJ'B. ROBERT GOTTSCELALK I Attesting OfficerCommissioner of Patents

